Selected fluorinated glycols



United States Patent M 3,337,644 SELECTED FLUORINATED GLYCOLS John J. Drysdale, Hockessin, Del., assignor to E. I. du Pont de Nemours and Company, Wilmington, Del., a corporation of Delaware No Drawing. Filed Dec. 14, 1965, Ser. No. 513,813 2 Claims. (Cl. 260-633) ABSTRACT OF THE DISCLOSURE Glycols of the general formula R CHOHCHOHR where R and R are perfluoro-, w-hydroperfluolo, or wchloroperfiuoroalkyl of 3-14 carbons, e.g., 4H,5H-tetradecafluoro-4,5-octanediol, useful as intermediates to fiuorinated condensation polyesters and as dispersing agents.

Related applications This application is a continuation-in-part of my copending application Ser. No. 136,202, filed Sept. 6, 1961, and now US. Patent 3,240,811, itself a continuationinpart of my copending application Ser. No. 825,631, filed June 19, 1959, and now US. Patent 3,012,069.

Field and summary of the invention This invention relates to, and has as its principal object provision of, new polyfluorinated 1,2-glycols.

In my above-mentioned Patent 3,012,069, the reaction of polyfluoroacyl halides with nickel carbonyl in the presence of benzonitrile at temperatures below 40 C. is

in which R and R are perfluoro-, w-hydroperfluoro-, or w-chloroperfluoroalkyl radicals of 3-14 carbons. These novel polyfluorinated 1,2-diglycols, also called et-glycols, can readily be obtained by reduction of any of the polyfiuorinated acyloin esters or enediol diesters of Patent 3,012,069 or the derived acyloins of Patent 3,240,811.

Reduction of the precursor acyloin esters, enediol diesters and derived acyloins to the 1,2- (or w) glycols can be carried out by any conventional chemical means and is most simply effected by hydrogen itself. Reaction conditions can vary as known to those skilled in the hydrogenation art. With these polyfluorinated acyloin esters, enediol diesters, and acyloins, reduction to the polyfluorinated a-glycols can be effected under the mildest of conditions, e.g., room temperature at 40 1b. hydrogen pressure or thereabouts. Generally some kind of inert reaction medium will be used, such as acetic acid. Catalysts may be used to effect the reaction faster under even milder techniques. With some of the longer chain polyfluorinated acyloin esters, polyfluorinated enediol diesters, and polyfluorinated acyloins, higher temperatures and higher hydrogen pressures will be required, but normally the reduction to the polyfluorinated a-glycols will 3,337,644 Patented Aug. 22, 1967 not require conditions appreciably more stringent than 100 C. at 1000 lb. hydrogen pressure.

Examples of the new polyfiuorinated a-glycols that may be obtained readily by the reduction of suitable acyloin ester, enediol ester or derived acyloin precursors by essentially the procedure of the example below include:

6H,7H-docosafiuoro-6,7-dodecanediol from 7H docosafluoro-6-oxo 7 dodecyl perfluorohexanoate or 7H- docosafluoro-7-hydroxy-6-dodecanone;

1H,7H,8H,14H-tetracosafluoro-7,8 tetradecanediol from 1H,14H-tetracosafluoro-7-tetradecene-7,8 diol di(7H- dodecafluoroheptanoate);

1H,11H,12H,22H-tetraoontafluoro 11,12 docosanediol from 1H,12H,22H tetracontafluoro-12-hydroxy 11- docosanone;

5H,6H,1,10-dichlorohexadecafluoro5,6 decanediol from 1,10 dichloro-5-decene-5,6Tdio1 di(5-chlorooctafluorovalerate) or 1,10-dichlorohexadecafluoro-6-hydroxy-5- decanone; I

15H,16H-hexapentac0ntafiuoro 15,16 triacontanediol from 16H hexapentacontafluoro-l6-hydroxy-15 triacontanone;

1H,9H,10H,18H dotriacontafiuoro-9,10-octadecanedi0l from 1H,10H,18H dotriacontafluoro 9-oxo-10-octadecyl 9H-hexadecafluoro-nonanoate;

. 7H,8H,1,14-dichlorotetracosafluoro 7,8 tetradecanediol from 8H,l,14 dichlorotetracosafluoro-7-oxo-8-tetradecyl 7-chlorododecafluoroheptanoate;

1H,15H,16H,3OH-hexapentacontafiuoro-15,16 triacontanediol from 1H,16H,30H-hexapentacontafiuoro-15- oxo-16-triacontyl 15H octacosafluoropentadecanoate;

4H,5H,1,8-dichlorododecafluoro-4,5-0ctanedi0l from 1,8- dichlorododecafluoro 4 octene-4,5-dio1 di(3-chl0rohexafluorobutyrate) 9H,IOH-tetratriacontafiuoro 9,10 octadecanediol from perfiuoro-9-octadecene-9,10 diol di(perfluorononanoate);

and 15H,16H,1,30-dichlorohexapentacontafluoro 15,16- triacontanediol from 1,30 dichlorohexapentacontafiuoro-lS-triacontene-l5,16-dio1 di(15 chlorooctacosafluoropentadecanoate) Embodiment of the invention There follows a nonlimiting example submitted to illustrate further the present invention. In this example, unless otherwise indicated all pressures are ambient atmospheric and all parts are by weight.

EXAMPLE A mixture of 11.2 parts of the enediol diester perfluoro- 4-octene-4,5-diol di(perfiuorobutyrate) (see Examples III and IV of Patent 3,012,069), 105 parts of acetic acid, and 0.2 part of 10% palladium-on-carbon catalyst was shaken in a conventional glass hydrogenation apparatus under 40 lb./ sq. in. hydrogen pressure at room temperature for 18 hours. The resulting reaction mixture was vented to the atmosphere, removed from the reactor, filtered, and the filtrate was diluted with 200 parts of water saturated with sodium chloride. The resultant mixture was extracted with about 70 parts of diethyl ether. After removal of the diethyl ether from the ether extract and subsequent purification by distillation, there was obtained 4H,5H-tetradecafluoro-4,5-octanediol as a clear, colorless liquid boiling at C. under a pressure corresponding to 25 mm. of mercury. On standing, the dihydrotetradecafluorooctanediol solidified. Recrystallization from chloroform afiorded pure 4H,5H-tetradecafluoro-4,5-octanediol in 50% yield as a white crystalline solid melting at 7173 C. Flourine and proton nuclear magnetic resonance were consistent with the dihydrotetradecafiuorooctanediol structure.

Analysis.Calcd. for C H F O F, 66.8%. Found: F, 66.4%.

The polyfiuorinated 1,2- or a-glycols of this invention have obvious utility as intermediates in the formation of polyfluorosubstituted condensation polyesters. For example, solid linear polyesters with dibasic acids such as adipic or terephthalic acids can be prepared from the oc-glYCOlS and the dimethyl esters of the acids by wellknown ester interchange procedures. These polyesters have the usual utilities of such, e.g., in forming films, fibers and the like. The glycols are also useful as surfactants, i.e., dispersing agents, particularly for waxes, oils, and greases, and especially for the polyfiuorinated low molecular weight polymers.

Since obvious modifications and equivalents in the invention will be evident to those skilled in the chemical arts, I propose to be bound solely by the appended claims.

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A compound of the formula OH OH R CC R 1'1 It References Cited UNITED STATES PATENTS 3,012,069 12/1961 Drysdale 260-633 3,129,053 4/1964 Castle 260633 3,240,811 3/1966 Drysdale 260593 LEON ZITVER, Primaly Examiner.

BERNARD HELFIN, Examiner.

I. E. EVANS, Assistant Examiner. 

1. A COMPOUND OF THE FORMULA
 2. THE COMPOUND OF CLAIM 1 IN WHICH R1 AND R2 ARE PERFLUOROPROPYL, SAID COMPOUND BEING 4H, 5H-TETRADECAFLUORO-4,5-OCTANEDIOL. 